Plasma injection method

ABSTRACT

The plasma spraying method is a coating method in which a material to be coated is sprayed onto a surface of a metallic substrate ( 2 ) in the form of a powder beam. The coating material is injected at a low process pressure, which is lower than 10,000 Pa, into a plasma defocusing the powder beam and is there partly or fully melted. In this connection, a plasma with sufficiently high specific enthalpy is produced so that a substantial portion, amounting to at least 5% by weight, of the coating material changes into the vapour phase and an anisotropically structured coating ( 1 ) is produced on the substrate. An anisotropic structured layer of the coating material is deposited on the substrate. In this coating, elongate particles ( 10 ), which form an anisotropic micro-structure, are aligned standing largely perpendicular to the substrate surface and low-material transitional zones ( 11, 12 ) bound the particles from one another.

The invention relates to a plasma spraying method in accordance with the preamble of claim 1. The generic process, described in U.S. Pat. No. 5,853,815 is a thermal spraying for the manufacture of a so-called LPPS (=low pressure plasma spraying) thin film. The invention also relates to applications of the method and to components which are coated in accordance with the method in accordance with the invention.

A conventional LPPS plasma spraying process is modified in the technical process by the LPPS thin film process, with a space through which plasma flows (“plasma flame” or “plasma beam”) being expanded due to the changes and extended to a length of up to 2.5 m. The geometrical extension of the plasma results in a uniform expansion—a “defocusing”—of a powder beam which is injected into the plasma with a delivery gas. The material of the powder beam, which disperses to form a cloud in the plasma and is partly or fully melted there, reaches a widely extended surface of a substrate in a uniform distribution. A thin film is formed on the substrate and its coating thickness is less than 10 μm and it forms a compact covering thanks to the uniform distribution. A thicker coating with special features can be produced by a multiple application of thin films, which makes such a coating usable as a functional coating. A porous coating can, for example, be produced using a multiple application and is suitable as a support for catalytically active materials (see EP-A-1 034 843=P.6947). A functional coating, which is applied to a base body forming the substrate, as a rule includes different part coatings. For example, for a gas turbine (stationary gas turbine or aeroplane power plant), which is operated at high process temperatures, the blades are coated with a first single coating or multi-layer part coating which produces resistance to hot gas corrosion. A second coating, which is applied to the first part coating and for which ceramic material is used, forms a heat insulating coating. The LPPS plasma spraying process is suitable for the manufacturing of the first coating. The heat insulation coating is advantageously produced with a process in which a coating with a columnar micro-structure is created. The coating thus structured is composed approximately of cylindrical small bodies or particles whose central axes are aligned perpendicular to the substrate surface. Transitional zones in which the density of the deposited material is lower than in the particles bound the particles at the side. A coating which has an anisotropic micro-structure in this manner is tolerant in expansion with respect to changing strains which result due to repeatedly occurring temperature changes. The coating reacts to the changing strains in a largely reversible manner, i.e. without forming cracks, so that its service life can be considerably extended in comparison with the service life of a customary coating having no columnar micro-structure.

The anisotropic micro-structure can be produced using a thin-film method which is a vapour deposition method. In this process, which is termed “EB PVD” (electron beam physical vapour deposition), the substance to be deposited for the heat insulating coating is brought into the vapour phase by an electron beam in a high vacuum and condensed from said phase onto the component to be coated. If the process parameters are suitably selected, a columnar micro-structure thus results. A disadvantage of this vapour deposition process is the high plant cost. In addition, the same plant cannot be used for the LPPS plasma spraying process and for the EB PVD process in the manufacture of a coating including a plurality of partial coatings. A plurality of work cycles must therefore be carried out for the coating.

It is the object of the invention to provide a plasma spraying method with which a heat insulating coating can be produced and which allows a coating, which includes the heat insulating coating as a part coating, to be applied to a substrate in one working cycle. This object is satisfied by the plasma spraying method defined in claim 1.

The plasma spraying method is a coating method in which a material to be coated is sprayed onto a surface of a metallic substrate in the form of a powder beam. The coating material is injected into a plasma defocusing the powder beam at a low process pressure, which is lower than 10,000 Pa and is partly or fully melted there, with a plasma being produced with a sufficiently high specific enthalpy such that a substantial portion—amounting to at least 5 percent by weight—of the coating material changes to the vapour phase and an anisotropically structured coating is formed on the substrate. An anisotropically structured layer of the coating material is deposited on the substrate. In this coating, elongate particles, which form an anisotropic micro-structure, are aligned standing largely perpendicular to the substrate surface. Low-material transitional zones bound the particles from one another.

The method in accordance with the invention has a further advantage with respect to the known method with which a coating structured in a columnar manner is produced by means of EB PVD: the process times for coatings of the same thickness are a lot shorter.

Dependent claims 2 to 5 relate to advantageous embodiments of the plasma spraying method in accordance with the invention. Application possibilities for the method in accordance with the invention form the subject of claim 6 and claim 7. Claims 8 to 10 relate to components coated in accordance with the invention.

The invention will be described in the following with reference to the drawings. There are shown:

FIG. 1 an anisotropically structured coating, manufactured by the method in accordance with the invention and drawn in accordance with a grinding pattern;

FIG. 2 a corresponding second coating which has been formed after an unfavourable change of a process parameter;

FIG. 3 a third coating, in which an anisotropic micro-structure can no longer be recognised after a further change of the same process parameter; and

FIG. 4 a schematic representation of a coating system comprising a heat insulation coating.

In FIG. 1, a section is shown through a coating 1 which was made using the method in accordance with the invention and which is drawn in accordance with a grinding pattern. The coating 1 deposited onto a substrate 2 with the LPPS thin film process, has an anisotropic structure and a coating thickness of around 150 μm. The anisotropic micro-structure is formed by elongate particles 10 which stand largely perpendicular to the substrate surface. Low-material transitional zones 12, which are drawn as lines, and gap-shaped intermediate spaces 11 bound the particles 10 from one another. Zirconium oxide stabilised with yttrium Y, namely

ZrO₂-8%Y₂O₃, were used as the coating material. The substrate 2 is as a rule an adhesion promoting coating or a protection coating against corrosion.

So that the anisotropic micro-structure arises, a plasma must be produced with sufficiently high specific enthalpy so that a substantial portion—amounting to at least 5% by weight, of the coating material changes into the vapour phase. The portion of the vaporised material which may not fully change into the vapour phase can amount to up to 70%. The plasma is produced in a burner with an electrical DC current and by means of a pin cathode or of a ring-like anode. The power supplied to the plasma, the effective power, must be determined empirically with respect to the resulting coating structure. The effective power given by the difference between the electrical power and the heat led away by cooling is, according to experience, in the range from 40 to 80 kW.

For the process pressure of the plasma spraying method in accordance with the invention, a value between 50 and 2000 Pa is selected, preferably between 100 and 800 Pa. A powder beam is injected into the plasma with a delivery gas. The process gas for the production of the plasma is a mixture of inert gases, in particular a mixture of argon Ar and helium He, with the volume ratio of Ar to He advantageously lying in the range from 2:1 to 1:4. The total gas flow is in the range from 30 to 150 SLPM (standard litres per minute). The powder conveying rate lies between 5 and 60 g/min, preferably between 10 and 40 g/min. The powder beam is shaped into a cloud of vapour and particles in the defocusing plasma. The substrate is preferably moved with rotating or pivoting movements relative to this cloud during the material application. In this connection, the heat insulating coating is built up by depositing a plurality of layers. The total coating thickness has values between 20 and 1000 μm, preferably values of at least 100 μm.

An oxide ceramic material, or a material which includes oxide ceramic components, is suitable for the manufacture of a heat insulating coating using the method in accordance with the invention, with the oxide ceramic material being in particular a zirconium oxide, in particular as zirconium oxide which is fully or partly stabilised with yttrium, cerium or other rare earths. The material used as the stabiliser is added to the zirconium oxide as an alloy in the form of an oxide of the rare earths, for example yttrium Y, cerium or scandium, with—for the example of Y—the oxide forming a portion of 5 to 20% by weight.

So that the powder beam is reshaped by the defocusing plasma into a cloud of vapour and particles from which a coating results with the desired micro-structure, the powdery starting material must be of a very fine grain. The size distribution of the powder particles is determined by means of a laser scattering method. For this size distribution, it must apply that it lies to a substantial portion in the range between 1 and 50 μm, preferably between 3 and 25 μm. Various methods can be used to manufacture the powder particles: for example spray drying or a combination of melting and subsequent breaking and/or grinding of the solidified melt.

With the coating shown in FIG. 1,which shows a well formed columnar micro-structure, the following values were used for the process parameters: process pressure=150 Pa; process gas=Ar, 35 SLPM, and He, 60 SLPM; powder conveying: conveying rate=20 g/min; spray distance=900 mm.

After an increase of the conveying rate to 40-50 g/min, and without the other parameters being changed, the coating 1′ shown in FIG. 2 is obtained. The micro-structure is still formed in a columnar fashion in part; however, it is no longer suitable for use as a heating insulating coating with very high resistance with respect to thermal changing stress. After a further increase of the conveying rate to values larger than 60 g/min—see coating 1″ in FIG. 3—the columnar micro-structure has completely disappeared. An increase of the process pressure or of the gas flow results also results in a disappearance of the columnar micro-structure. Interestingly, a profiled surface is formed with very pronounced rises, with these having been formed over rises of the substrate 2. It can also be recognised from coatings 1, 1′ of FIGS. 1 and 2 that a similar connection exists between the anisotropic micro-structure and the surface profile of the substrate 2: the elongate particles 10 preferably start from rises of the substrate 2.

The heat insulating coating system shown schematically in FIG. 4 was applied to a base body 3 by means of LPPS thin film processes. This coating system is comprised of a barrier coating 3 a, a hot gas corrosion protection coating 4, a heat insulating coating 1 on a ceramic base and applied in accordance with the invention and a cover coating 5 which, as a smoothing coating, improves the erosion resistance. Additionally, a protection coating (not shown) on an oxide base can be provided between the hot gas corrosion protection coating 4 and the heat insulating coating 1.

The base coating consisting of the barrier coating 3 a and the hot gas corrosion protection coating 4 has a coating thickness whose value is between 10 and 300 μm, preferably between 25 and 150 μm. For the barrier coating 3 a, an NiAl alloy or an NiCr alloy is, for example, deposited on the base body 3 which can consist of an Ni or Co base alloy. The hot gas corrosion protection coating 4 in particular consists, at least in part, of a metal aluminide, of an MeCrAlY alloy, with Me standing for one of the metals Fe, Co or Ni or of a ceramic oxide material. It preferably has an either dense, columnar, directional or unidirectional structure. The: base coating 3 a, 4 forms the substrate of the heat insulating coating 4 which is produced in accordance with the invention and thus has a columnar micro-structure. The smoothing coating 5, whose coating thickness has a value between 1 and 50 μm, preferably between 10 and 30 μm, consists in particular at least in part of the same material as or of a similar material to the heat insulating coating. The part layers of the coating system are preferably all applied in a single work cycle without interruption by LPPS thin film processes. After the application, the coating system can be heat treated as a whole.

In the plasma spraying process of the invention an additional heat source can also be used in order to carry out the deposition of the coating material within a predetermined temperature range. The temperature is preset in the range between 300 and 900° C., preferably in the temperature range 450 to 750° C. An infrared lamp or plasma jet can, for example, be used as an auxiliary heat source. In this arrangement a supply of heat from the heat source and the temperature in the substrate which is to be coated can be controlled or regulated independently of the already named process parameters. The temperature control can be carried out with usual measuring methods (using infrared sensors, thermal sensors, etc.).

The method in accordance with the invention can be used to coat components exposed to high process temperatures with a heat insulating coating system. Such components are, for example, components of a stationary gas turbine or of an aeroplane power plant: namely turbine blades, in particular guide blades or runner blades, or even components which can be exposed to hot gas such as a heat shield.

A porous support structure for catalytically active materials can also be produced using the plasma spraying method in accordance with the invention and can be used in a heterogenic catalyst. 

1. A plasma spraying method in which a coating material in the form of a powder beam is sprayed onto a surface of a metallic substrate (2), wherein the coating material is injected at a low process pressure, which is lower than 10,000 PA, into a plasma defocusing the powder beam and is there partly or fully melted, characterised in that a plasma with sufficiently high specific enthalpy is produced so that a substantial portion, amounting to at least 5% by weight, of the coating material changes to the vapour phase and an anisotropically structured coating (1) is produced on the substrate with the coating material, with elongate particles (10), which form an anisotropic micro-structure, being aligned standing largely perpendicular to the substrate surface and low-material transitional zones (11, 12) bounding the particles from one another.
 2. A plasma spraying method in accordance with claim 1, characterised in that the anisotropically structured coating (1) is a heat insulating coating which is used, for example, in a gas turbine and whose coating thickness has values between 20 and 1000 μm, preferably values of at least 100 μm; and in that the coating is built up from a plurality of layers during manufacture.
 3. A plasma spraying method in accordance with claim 1, characterised in that a) a value is selected for the process pressure between 50 and 2000 Pa, preferably between 100 and 800 Pa and the specific enthalpy of the plasma is produced by emitting an effective power which has to be determined empirically and which, according to experience, is in the range from 40 to 80 Kw; b) the powder beam is injected into the plasma with a delivery gas, the process gas being a mixture of inert gases, in particular a mixture of argon Ar and helium He, with the volume ratio of Ar to He advantageously lying in the range from 2:1 to 1:4 and the total gas flow lying in the range from 30 to 150 SLPM; c) the powder delivery rate is between 5 and 60 g/min, preferably between 10 and 40 g/min; and d) the substrate is preferably moved with rotational or pivotal movements relative to a cloud of the defocused powder beam during the material application.
 4. A plasma spraying method in accordance with claim 1, characterised in that a material is used for the coating which includes oxide ceramic components, with such a component being in particular a zirconium oxide fully or partly stabilised with yttrium, cerium or other rare earths and the material used as the stabiliser being added as an alloy to the zirconium oxide in the form of an oxide of the said rare earths.
 5. A plasma spraying method in accordance with claim 4, characterised in that, for the powdery coating material, the size distribution of the powder particles is determined by means of a laser scattering method; and in that this size distribution lies to a substantial amount in the range between 1 and 50 μm, preferably between 3 and 25 μm, with in particular spray drying or a combination of melting and subsequent breaking and/or grinding being used as the method of manufacturing the powder particles.
 6. A plasma spraying method in accordance with claim 1, characterised in that an additional heat source is used in order to be able to carry out the deposition of the coating material within a predetermined temperature range, with a heat input of the heat source and the temperature in the substrate to be coated being controlled or regulated independently of the already named process parameters.
 7. Use of the plasma spraying method in accordance with claim 1 for producing a coating which includes at least one layer (1), in particular a heat insulating layer, having anisotropically structured, elongate particles (10).
 8. Use in accordance with claim 6, characterised in that the coating forms a heat insulating coating system (3 a, 4, 1, 5) which includes, in addition to the heat insulating coating (1), a base coating (3 a, 4) between a base body (3) and the heat insulating coating and/or a cover coating (5) on the heat insulating coating, wherein a) the base layer includes a hot gas corrosion protection coating (4), whose coating thickness has a value between 10 and 300 μm, preferably between 25 and 150 μm, and which consists, in particular at least in part, of either a metal alumnide of an MeCrAlY alloy, with Me standing for one of the metals Fe, Co or Ni, or of a ceramic oxide material which preferably has an either dense, columnar, directional or unidirectional structure, b) the cover coating is a smoothing coating whose coating thickness has a value between 1 and 50 μm, preferably between 10 and 30 μm, and which in particular consists at least in part of the same material as or a similar material to the heat insulating coating; and c) the part coatings of the coating system are preferably all applied in a single work cycle by LPPS thin film processes.
 9. A component which is coated by application of a coating or of a plurality of coatings (3 a, 4, 1, 5) onto a base body (3) by means of the plasma spraying method in accordance with claim 1, wherein in particular the base body consists of an Ni base alloy or of a Co base alloy.
 10. A component in accordance with claim 8, characterised in that a coating system (3 a, 4, 1, 5) applied to the base body (3) has been subjected to a heat treatment after the carrying out of the coating processes.
 11. A component in accordance with claim 8, characterised in that it is a component of a stationary gas turbine or of an aeroplane power plant, namely a turbine vane, in particular a guide vane or a turbine blade, or a component which can be exposed to hot gas, for example a heat shield. 